Water soluble condensation product and process for preparing the same



Patented May 30, 1933 UNITED STATES PATENT OFFICE KARL nAcnLAUEn ANDcnnrsrorn woman, on HocHs'r-on-THE-MAIN, 'ena vraiiY,

ASSIGNORS no I. e, raannnrnnusrnrn AK'lIENGESELLSCI-IAFT, or nnnnxronrON-THE-MAIN, GERMANY, A coaroaa'rron on GERMANY WATER SOLUBLECONDENSA'IION PRODUCT AND PROCESS FOR PREPARING-THE SAME No Drawing.Application filed April 15, 1926, Serial No. 102,331, and in GermanyApri123, 1925.

WVe have found that aromatic hydroxy alcohols including derivatives andsubstitution products thereof, can be condensed with aromatic sulfonicacids by a very simple and easy method which permits working attemperatures up to 100 C. and above and in certain cases, in presence ofstrong mineral acids. Various methods may be employed for themanufacture of the said, hitherto unknown, compounds, which possess veryvaluable properties and can be used for instance as tanning substances,frothing and emulsifying agents, intermediate products for makingdyestufi's etc. They are also capable of producing on the animal fibreefficient resists against dyestufis. Products of the said kind may alsobe obtained by condensing aromatic sulfonic acids with mixtures ofhydroxy alcohols and other compounds suitable for the condensationprocess-such as aliphatic, aromatic or hydroaromatic alcohols, phenolsor compounds with replaceable halogen atoms (benzylchloride,dichlorhydronaphthalene, benzoylchloride, ethyl chloride or the like).Or there may be used as starting material higher molecular aromaticsulfonic acids, obtainable, for instance, by condensation of aro maticsulfonic acids with aldehydes or compounds capable of splitting offaldehyde, or with any other compounds capable of condensing with thearomatic nucleus with formation of C' or S'1inkages. Instead of usingfor the reaction mixtures of hydroxy alcohols and the above specifiedcompounds,

; it may sometimes be advantageous to effect the condensation with theseveral components in a determined order of succession. Com pounds ofvaluable properties may also be obtained by subsequent condensationofproducts, which, according to our inventive idea, are produced, forinstance, fromaromatic sulfonic acids and hydroxy alcohols, with nucleusbinding compounds (aldehydes,'sulfuryl chlorides etc.). Instead of thearomatic sulfonic acids or aromatic hydroxy alcohols above referred to,there may, as is obvious to every chemist, also beused the derivativesand substitution products of these compounds.

The following examples serve to illustrate our invention all parts beingby weight. I

(1) 10 parts of naphthalene are sulfonated with 16 parts of sulfuricacid (98%) at 160, C. Into the mixture when it has cooled to thetemperature of the water bath, are run, while vigorously stirring, 19,4:parts of hydroxybenzyl alcohol. After the latter is completelyintroduced, the whole is again stirred for a short time in order toaccomplish the reaction. V I I The condensation product is to be treatedwith caustic soda solution of 20% strength until it has an acidity suchthat lgram is equivalent to 10 com. of n/lO NaOH. The water solution canbe used for tanning purposes. It makes leather white and verysoft andimparts to it a feel like kid-leather.

" Instead of hydroxybenzyl alcohol there may be used other hydroxyalcohols, forinstance alcohols produced fromcresol.

(2) 10 parts of naphthalene are sulfonated according to the indicationscontained in German Patent No. 292,531 with-12,5 parts of sulfuric acid(98%) at 130-140 .and'then condensed with 4: parts of formaldehyde of30% strength at 80 C. Towards-the end of the reaction so much ofsulfuric acid (7 0%) is added that the mass can still be easily stirred,whereupon 9,7 parts of p-homosaligenin are run into it at vwater-bathtemperature. Afterhaving again stirred for a short time, the reaction iscomplete. The product thus obtained is soluble in water to a clearsolution and after being treated with caustic soda solutionof 20%strength until it has an acidity such that 1 gram is equivalent to 10com. ofn/10 NaOH, it yields a tanning substance which makes leather softand white.. This product is considerably superior to thedinaphthylmethane-disulfonic acid as regards its tanning effect.

[(3) Into the sulfonation mixture prepared according to Example 1 from10 parts of naphthalene and. 16 parts of-sulfuricacid are run atwater-bath temperature, while well stirring, 21,5 parts ofhydroxyphenylethyl ialcohol. After having again stirred the massforashort time, the reaction is complete and the 'resultingsolutionafter it hasbeen 'neutralized with caustic soda solution of 20% strengthuntil it has an acidity such that 1 gram is equivalent to 8 com. of n/10NaOH, can be directly used as tanning liquor.

11 P r s f. me yl ap h le e are converted by means of 16 parts ofsulfuric acid (98%) at 120 G. into methylnaphtha: lene sulfonic acid andtheir condensed at wa-i ter-bath temperature, while well stirring,

with 19,4 parts of hydroxybenzyl alcohol. The condensation product,after being neuralize un il it has acid y su h t 1 gram is equivalent to10 com. of n/lO NaOH, constitutes a valuable tanning material.

(5) Into the sulfonation mixture prepared according to Example 1 from 10parts of naphthalene and 12' parts of sulfuric acid (98%) is run atwa'tenbath temperature, while well stirring, a mixture of 9,7 parts ofp-homosaligenin and 7,3 parts of phenol. After the main reaction hastaken place, the mass is heated for a short time to a somewhat highertemperature in order to complete the reaction.

Thus a condensation product is obtained which, after being neutralizedwith caustic soda solution of 20% strength until it has an acidity suchthat 1 gram is equivalent to 10 com. of n/lO NaOH, can be used as atanning liquor.

(6) 64 parts of naphthalene are condensed with 63 parts of benzylchloride and sulfonated with a mixture of 28 parts of oleum (20%) and75. parts of ohlorosulfonic acid at 80-90.

10 parts ofthe resulting mixture are. condensed with 3,3 partshydroxybenzyl alcohol at 95. After being neutralized with caustic sodasolution of 20% strength until it has an acidity such that 1 gramisequivalent to 10 ccm. of n/10 NaOH, the resulting product is soluble inWater to a perfectly clear solution which can be used for tanningpurposes. The leather prepared therewith is white, soft and full bodied.

(7) Into a mixture of 12,8 parts of'naphthalene and 4,6 parts of ethylalcohol are slowly introduced by drops at C. 30 parts of chlorsulfonicacid. After having continued the stirring of the mass for a prolongedtime at 100120 C. the condensation is complete. Into 10 parts of theresulting mixture are then run at 9510.0 C. 3,3 parts of hydroxybenzylalcohol. The. product is partly neutralized with caustic soda solutionof 20% strength until it has an acidity such that 1 gram is equivalentto 11 com. of n/lO NaOH' and is then suitable for the preparation of agood leather.

(8) 12,8 parts of naphthalene are condensed with"12,6 parts ofbenzylchloride to which 0,002 part of crude zinc dust hasbeen added andthe mass is then sulfonated at 90100 with 17 parts of oleum of 20%strength. Into the sulfonation mixture is run at about 100 C., whilewell stirring, a mixture of 10,8 parts of methylhydroxybenzyl-alcoholCH3.CuHz

crnon and 2,4 parts of hydroxybenzyl-alcohol.

When the condensation is complete, the product is treated with causticsoda solution of 20% strength until it has an acidity such that 1 gramis equivalent to 10 com. of n/l0 NaOH; it is suitable fortanningpurposes.

(9) 38,4 parts of naphthalene are con- V densed at 170-190 with 42 partsof benzoylchloride to which is added about 0,05 parts of crude zinc dust(at'170l90). The condensation product is fractionated in vacuo under 37mm. pressure. 17,0 parts of the fraction distilling over at 150210, aresul-' fonated with 22,4 parts of oleum (20%) at 140 and then condensedat 100 0., while well stirring, with 9,1 parts of hydroxybenzylalcohol.

After the product has been treated with caustic soda solution of 40%strength until it has an acidity such that 1 gram is equivalent to 7com. of 11/10 NaOH, it can be used for tanning purposes.

(10) 8,8 parts of tetrahydronaphthaline are sulfonated with 12 parts ofsulfuric acid (98%) at 100 and then condensed with a mixture of 7,1parts of methylhydroxybenzyl alcohol CHa.CaH3

oinon and 1,6 parts of hydroxybenzyl alcohol at a like temperature.After the product has been treated with caustic soda solution of l beingtreated with caustic soda solution. of

20% strength until ithas an acidityv such that 1 gram is equivalent to5ccm. of n/1 0 NaOH, is ready for use as tanning material.

(12) 25 parts of the sulfonation mixture of naphthalene and sulfuricacid are condensed first with 5,0 parts of cyclohexanol at 120 C. andthen with 12,2 parts of hydroxybenzyl-alcohol at 100 C. After theproduct has been treated with caustic soda solution of 20% strengthuntil it has an acidity of about such that 1 gram is equivalent to 10com. of 11/10 NaOH, it is ready for use as tanning material.

(13) Into 31,3 parts of the sulfonationv mixture, obtained according toExample 10 from tetrahydronaphthalene and sulfuric acid, chlorine isintroduced until the weight of the mixture has increased by 2,9 parts.

8,0 parts of the resulting chlorination-mixture are condensed with 6,2parts of hydroxybenzyl alcohol and the product is treated with causticsoda solution of 20% strength until it has an acidity such that 1 gramis equivalent to 10 com. of n/10 NaOH, whereupon it can be used fortanning purposes.

(14) 16,3 parts of a-chlornaphthalene are sulfonated with 25,5 parts ofoleum f strength at 150 C. and then condensed at 100 with 12,4 parts ofhydroxybenzyl alcohol. After the product has been treated with causticsoda solution of 20% strength until it has an acidity such that 1 gramis equivalent to ccm. of n/10 NaOH, it can be used as tanning material.

(15) 25 parts of the sulfonation mixture obtained according to Example 1from naphthalene and sulfuric acid are first condensed with 3,0 parts ofisopropyl alcohol at 100 and then with 12,2 parts of hydroxybenzylalcohol at a like temperature.

After the product has been treated with caustic soda solution ofstrength until it has an acidity such that 1 gram is equivalent to 10ccm. of n/10 NaOH it can be used as tanning material.

(16) parts of benzene are run into parts of sulfuric acid of 100%strength, while stirring, and the mixture is finally heated to 100 (3.,20 parts of this mixture are condensed at 100 C. with 16A parts ofhydroxybenzyl alcohol and treated with caustic soda solution of 20%strength until, it has an acidity such that 1 gram is equivalent to 9com. of n/10 NaOH. The product can be used for tanning urposes.

(17 22,6 parts of crystallized naphthalenesulfonic acid are condensedwith 6,8 parts of sulfur mono-chloride at 100 C. and mixed and stirredwith 10,6 parts of sulfuric acid (95%) 18 parts of this mixture arecondensed at 100 C. with 6,2 parts of hydroxybenzyl alcohol and treatedwith caustic soda solution of 20% strength until it has an acidity suchthat 1 gram is equivalent to- 9 com. of n/10 NaOH; it can then be usedas a tanning material.

(18) 10 parts of the residual mass, obtained during the process ofpurifying anthracene, are sulfonated with 15 parts of concentratedsulfuric acid at 140 C. andcondensed at 100 C. with 7 parts of hydroxybenzyl alcohol. The product is treated with caustic soda solution of 20%strength until it has an acidity such that 1 gram is equivalent to 10com. of n/10 NaOH, whereupon it can be used for tanning purposes.

l/Ve claim:

1. Process for preparing water-soluble condensation products whichconsists in condensing aromatic hydroxy alcohols with aromatic sulfonicacids of the type BS0 13, R standing for a hydrocarbon radical.

'2. Tetrahydronaphthalene sulfonic acid compounds of the followingformula in which w stands for a number from 1 to 5, inclusive, saidproducts being capable of converting hides into well-plumped leather. 3.l/Vater-soluble aromatic sulfonic acid compounds of the followingformula:

in which R constitutes an aromatic radical, and R constitutes anaromatic radical containing at least one hydroxyl group, and in which mstands for the number from 1-5 inclusive, said products being capable ofconverting hides into well-plumped leather.

4:. Water-soluble tetrahydronaphthalene sulfonic acid compounds of thefollowing formula:

in which R constitutes an aromatic radical containing at least onehydroxyl group and in which 00 stands for the number from 1-5 inclusive,said products being capable of converting hides into well-plumpedleather. In witness whereof, we affix our signatures.

KARL DACHLAUER. CHRISTOPH THOMSEN.

